Abstract
All-valence-electron SCF calculations support the linear “sesquiacetylenic” geometry in propargylic dianions. The two accompanying univalent cations are close to the central carbon, with an angle MC2M of 90°. The migration of lithium in allylic systems is interpreted as an intramolecular sigmatropic rearrangement.
Zusammenfassung
SCF-Rechnungen unter Benutzung aller Valenzelektronen stützen die lineare “sesquiacetylen”-ähnliche Geometrie in Propargyldianionen. Die beiden zugehörigen Kationen befinden sich in der Nähe des zentralen Kohlenstoffatoms und bilden einen MC2M-Winkel von 90°. Die Wanderung des Lithiums in allylartigen Systemen wird als intramolekulare sigmatrope Umlagerung interpretiert.
Résumé
Des calculs SCF pour tous les électrons de valence sont en faveur de la géométrie linéaire «sesquiacétylénique» dans les dianions propargyliques. Les deux cations univalents correspondants sont proches du carbone central avec un angle MC2M de 90°. La migration du lithium dans les systèmes allyliques est interprétée comme un réarrangement intramoléculaire sigmatrope.
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Becker, J.Y., Meyer, A.Y. & Klein, J. Sesquiacetylenes. Theoret. Chim. Acta 29, 313–317 (1973). https://doi.org/10.1007/BF00532187
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DOI: https://doi.org/10.1007/BF00532187